Sf5 containing azomethines and their preparation



United States Patent 3,228,981 SF CONTAINING AZOMETHINES AND THEIR PREPARATION Charles W. Tullock, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed June 27, 1962, Ser. No. 205,562 17 Claims. (Cl. 260-543) This invention relates to, and has as its principal objects provision of, novel compositions of matter and the preparation of the same.

The principal compositions of this invention are defined by the general formula SF -N=CXX', in which X is halogen of atomic number 9 through 17 and X is a number of the group consisting of halogen of atomic number 9 through 17, hydrogen-free polyfluoroalkyl of up to 19 carbon atoms (preferably perfluoroor chloroperfluoroalkyl), aryl, chloroaryl, and nitroaryl of up to 14 carbon atoms,

SE5 F The compounds of the above formula wherein X is chlorine and X is either chlorine, polyfluoroalkyl, aryl, chloroaryl, nitroaryl, or

are made by subjecting a mixture of SF Cl and either cyanogen, cyanogen chloride, or a carbonitrile tree of aliphatic, i.e., nonaromatic, hydrogen, and aliphatic carbon-carbon unsaturation to the action of ultraviolet light.

The compound of the above general formula wherein X and X are both fluorine is made by reacting SF N=CCl with an alkali metal fluoride. The compounds in which X is fluorine and X is polyfluoroalkyl, i.e., R are made by reacting SF N=CClR with either hydrogen fluoride or an alkali metal fluoride. SF =CCl also reacts with hydrogen fluoride but yields the saturated product, SF NHCF The compound of the above formula in which X is fluorine and X is is synthesized by treating with sodium fluoride the product obtained from the reaction of SF Cl with cyanogen, i.e.,

as described below in Example 1V.

' In the process employing ultraviolet light, a mixture of SF Cl and either cyanogen, cyanogen chloride or carbonitrile is placed in a reactor, illuminated with ultraviolet light, (eg, from a mercury vapor lamp, and the product is recovered either as condensate on the bottom of the reactor or, if volatile enough, by transfer from the reactor to a cold evacuated receiver.

Nitriles useful in this process are cyanogen, cyanogen chloride, and carbonitriles of the formula ACN, in which A is polyfluoroalkyl radical of up to 19 carbon atoms free of aliphatic hydrogen, and preferably either perfluoroor chloroperfluoroalkyl, or aryl, chloroaryl, or nitroaryl of up to 14 carbon atoms. Usable specific carbonitriles include perfluoropropionitrile, perfluorobutyronitrile, perfluoroisobutyronitrile, perfluorocapronitrile, perfluorostearonitrile, S-chlorodecarfiuoropentanonitrile, 8-chlorotetradecafluoroctanonitrile, perfiuorocaprylonitrile, benzonitrile, chlorobenzonitrile, nitrobenzonitrile, and the like.

The reaction between SF Cl and carbonitrile is an addition generally involving one mole of each reactant and may be represented by the following equation:

SF Cl+ACN SF N= CClA in which A has the previously indicated meaning. Because of the dimeric nature of cyanogen, its similar reaction with SF CI requires two moles of the latter compound in accord with the equation:

of the commercially available lamps which are high in ultravlolet light output. Generally speaking, mercury vapor lamps are preferred because they provide a rela tively intense source of ultraviolet light. Many lamps of this type are available and include low and high pressure lamps with various types of envelopes. The most preferred types are those with quartz envelopes because such envelopes permit higher transmission of ultraviolet light.

In practice, it is desirable that the light source be as close to the mixture of SF Cl and other reactant as possible. This can be accomplished by placing the lamp immediately adjacent a transparent wall of the reaction vessel or in a well projecting into the reaction space, or by passing the mixture of reactants through a tube which is exposed to ultraviolet light.

The irradiation is carried out for periods of time which can be as short as 15 minutes or can extend to several days, depending upon the size of the sample being irradiated, the efliciency of the light source, and the nature of the reactants.

The reaction between SF Cl and either cyanogen, cyanogen chloride, or carbonitrile can be carried out in the gas or liquid phase at temperatures which can be up to C., but most generally are between -20 C. and 50 C. Pressures employed are usually autogenous as with all reactions of this invention. Externally applied pressure can be used, however, but leads to no practical advantage.

The reaction between the SF Cl and either cyanogen, cyanogen chloride, or carbonitrile can be carried out in the presence of an inert, normally liquid reaction medium. By inert reaction medium is meant a medium which is unreactive, under the conditions of reaction, with the reactants or reaction products.

When a reaction medium is used, it can equal or exceed the weight of the reactants by many fold. If the carbonitrile is normally liquid under the conditions of reaction, it can be used as a reaction medium and the excess removed after reaction is complete. Suitable reaction media are carbon tetrachloride, dichlorodifluoromethane trichlorofluoromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, and the like.

The reaction between SF5N CClRf or SF N CCI and HF is not catalyzed by ultraviolet light and involves reacting one mole of the pentafluoro compound with two or three mole-s of HP, in accord with the equations:

These reactions usually are carried out at temperatures ranging from 25 to C. and autogenous pressure for convenience, but reactions will proceed in some cases at atmospheric pressures using liquid hydrogen fluoride at 0 to +19 C. as a reaction medium.

The reaction between SF N:CCl SF N=CClR SF N CClCCl=NSF and alkali metal fluoride reand one or two moles of the alkali metal fluoride, in accord with the equations:

The alkali metal fluorides usable are sodium, potassium, rubidium, and cesium fluorides. Of these sodium fluoride is preferred because of its availability, reactivity, and low cost.

In a convenient way for effecting the reaction, the alkali metal fluoride is suspended in a suitable reaction medium, for example, tetramethylene sulfone and the SF N:CCl SF N=CClR or SF N=CClCCl=NF S compound is added to the suspension at ambient temperature. The reaction mixture is then heated rapidly up to about 50 C. and held between this temperature and 200 C., usually between 60 and 180 C., for from minutes to two hours. The product, if volatile, is collected in a trap cooled in an acetone solid-carbon dioxide bath and the condensate is subjected to fractional distillation to isolate the desired product. Another procedure involves removal of the metal chloride and unreacted metal fluoride by filtration, followed by distillation.

The products of this invention,, e.g., SF N CCl SF N=CClR and SF N=CFR are useful as solvents for low molecular weight polytetrafluoroethylenes. Fabrics or paper which have been dipped into solutions in these solvents, the solvents then removed by evaporation, have a thin coating of polytetrafluoroethylene, which im-parts thereto water repellency or, in some cases, improved resistance to flames. Polyamide resins in contact with these materials swell and on moderate warming become soft enough to be molded readily. High molecular weight polyoxymethylenes of the type disclosed and claimed in US. Pat. No. 2,768,994; dissolve in SF NHCF and SF NHR derivatives at room temperature, while polyamides are softened sufiiciently so that they can be shaped into desired forms. The substituted amine,

also is an excellent solvent for very low molecular weight polytetrafiuoroethylene at room temperature. The gaseous product, SF5N:CF is useful as a fumigant for roaches, flies, etc.

There follow some examples submitted to illustrate but not to limit the invention. In these examples the nuclear magnetic resonance, n-m-r, data were obtained using a high resolution spectrometer and associated electromagnet, both manufactured by Varian Associates, operating usually at 56.4 inc/sec. but sometimes at 40 inc/sec. and approximately 14,000 gauss. Quantitative analyses based on infrared or n-m-r are expressed as mole percentages.

- Example I A l2'-liter round bottom flask containing 14 g. of cyanogen chloride and 37 g. of sulfur chloride pentafluoride, SF CI, was irradiated for 6.5 hours at ambient temperature. The contents of the flask were then removed and allowed to warm gradually to attain ambient temperature. The liquid distilling above room temperature from this. experiment and that from a second one in which 14 g. of cyanogen chloride and 33 g. of SF Cl were irradiated for eight hours were composited to give 37 g. of product. This corresponded to a 38% conversion, based on SF Cl, of colorless SF N CCI (dichloromethylenearnino) sulfur pentafluoride, B.P. 86-88 C. The foreshot, B.P. 3586 C., amounting to 6.4g. was SF N CCI contaminated with a small amount of S F The product, (dichloromethyleneamino)sulfur pentafluoride, SF N=CC1 reacted with 10% sodium hydroxide solution to give a solution containing both chloride and fluoride ions.

Anwlysis.Calcd. for CCl F NS: Cl, 31.70; F, 42.41; S, 14.28. Found: Cl, 32.37; F, 42.44; S, 13.63.

The F n-m-r spectrum indicated that an SP group The infrared spectrum showed absorption was present. at 6.10 ,0. C N) and in the 10.5 to 12.0 ,u region (SP Mass spectrometric analysis was satisfactory. Peaks corresponding to the parent (223), to SP (127'), and to CCl (82) were found to be present. The alternate structure for this compound, SF CCI=NCL was eliminated when hydrogen fluoride was found to conert it to SF NHCF and sodium fluoride was found to convert it to SF N=CF Example II A 22-liter round bottom flask containing 38 g. of trifluoroace-tonitrile, CF CN, and 67 g. of SF Cl was irradiated for 14.5 hours at ambient temperature. Distillation of the liquid remaining after removal of unreacted CF CN and SF CI yielded 33 g.,- amounting to a 32% conversion based on CF CN, of colorless (l-chlorotrifluoroethylideneamino) sulfur pentafluoride,

SF5NICCICF3,

The alternate structure, SF CCF =NCL was eliminated when it was found that hydrogen fluoride converted the product to SF NHC F Example Ill A 22-liter round bottom flask containing 59 g. of por fluorobutyronitrile and 59 g. of SF Cl was irradiated for 17.7 hours at ambient temperature. Distillation of the product yielded 49 g., amounting to a 45% conversion, based on the C3F7CN used, of SF N=CCIC F (l-chloroheptafluorobutylideneamino)sulfur pentafluoride, B.P. 99- 101 C., and 18.4 g. of foreshot, B.P. 3297.5 C., which contained some S F a large amount of SF N=CCIC F and some SF N=CFC F (based on infrared and n-m-r analyses.

-Analysis.Calcd.-f0r C ClF NS: Cl, 9.93; F. 63.77. Found: Cl, 9.91; F, 62.24.

The F n-m-r spectrum indicated that an SP5 group and a C3F7 group were present. The infrared spectrum showed absorption at 5.92 C=N-) and in the 11 to 12 region (SP Example IV 2SF CI+ (CN) SF N=CCl-CCl= NSF A 22-liter round bottom flask containing 23 g. of cyanogen and 60 g. of SF CI was irradiated for 22 hours at ambient temperature. Removal of the gases left 25 g. (I) of yellow-colored liquid distilling above 25 C. A second experiment in which 22 g. of cyanogen and 62 g. of SF CI were irradiated for 23 hours yielding 33 g. (II) of crude product distilling above 25 C. The composite of experiments I and II on distillation yielded the followmg:

Cut No. 7 was SF N=CCl-CCl=NSF N,N'- (dichloroethanediylidene)bis(aminosulfur pentafluoride) (compound II), based on n-m-r analysis which indicated that a single SP group and no other fluorine was present. The infrared spectrum showed absorption at 6.10;; C=N-) and in the 11 to 12 region (SP Mass spectrometric analysis was satisfactory; although the parent peak was not present, peaks corresponding to the parent minus a chlorine (341), and to SF N=CC1 (188) were present.

Analysis.-Calcd. for C Cl F N S Cl, 18.8; F, 50.4; S, 17.0. Found: Cl, 19.78; F, 49.80; S, 16.47.

The F n-rn-r analysis suggested that Cuts Nos. 5 and 6 contained about 90% II and;10% of I, believed to be SF N=CC1CF=NSF The evidence for the structure of compound I is based on infrared, which showed absorption at 5.85;]. CF N) and at 6.05

and on mass spectrometric analysis, which showed the peak corresponding to the parent minus a chlorine (325) and a peak corresponding to SF N=CC1CF=N (233). Cut No. 3 was shown by mass spectrometric analysis to contain 30% SF N=CCl the remaining product being probably SF N CCICN, based on peaks corresponding to parent minus fluorine (195), and the parent minus chlorine 179). Infrared analysis also showed absorption at 4.45 for nitrile.

Unsuccessful attempts were SF N=CClCF=NSF (compound I) by a careful'r'edistillation of those cuts in which ,it was present in substantial amount. Mixtures of I and II when heated with sodium fluoride suspended in t etramethylenesulfone at temperatures up to 145 C. yielded'smallamounts (3.7 g.) of product, B.Pf1 l8-f120 C. The infrared spectrum of the product showed strong absorption at'5.8n (satis factory for CF N)) and in the 10.712 :region;

(SE F n-m-r spectrum showed the presence of an SP group and a C-F bond. Mass spectrometric analysis appeared satisfactory for SF N;CFCF=NSF N,N'- (difluoroethanediylidene bis amino'sulfur pentafluoride showing peaks corresponding to the parent (344), to the parent minus three fluorines (287), to

A 230-ml. quartz tube provided with a magnetic stirrer and attached to a solid carbon dioxide-acetone cooled niade to isolate pure 6 finger was charged with 27 g. of benzonitrile, C H CN, 10 ml. of 1,1,2-trichloro-1,2,2-trifluoroethane CFgClCF C1 (added to keep the C H CN in a liquid state), 45 g. of SF C1, and 7 g. of dichlorodifluoromethane, CF CI (added to prevent the SF Cl from solidfying in the cold finger), and the mixture exposed to a mercury resonance lamp for two days. Removal of the CF ClCFCI and CF Cl and unreacted benzonitrile under reduced pressure (B.P. 21-25 /0.2 mm.) left 1.9 g. of a viscous syrup. The F n-m-r spectrum indicated the presence of an SP group and no other fluorine; the infrared spectrum showed broad absorption at 10.7 to 125 (SP and a probable 6.2 band; benzonitrile also was shown to be present. A test portion of the sample on warming with 10% sodium hydroxide solution gave a solution containing chloride ion. Mass spectrometric analysis was fairly satisfactory for SF N CCIC H (phenylchloromethyleneamino)su1fur pentafluoride, since peaks corresponding to the parent (265) and to the parent minus chlorine (230) were present. In addition, the presence of C H CN and of C1C H CN was confirmed. The presence of very small peaks at 391 and 390 provided evidence for the possible presence of SF N CClC I-I SF Example VI SF N=CCI 2NaF SF N CF 2NaCl To a suspension of 25 g. of sodium fluoride in 50 ml. of tetramethylene sulfone was added 17.8 g. of

SF N=CCl at ambient temperature. The mixture was rapidly heated to 75 C. and then at 75156 C. for 0.75

hour, during which time the volatile products removed Were collected in a solid carbon dioxide-acetone cooled trap. The volatile material thus obtained was combined with that from a second experiment using 24 g. SF N=CCl Distillation of the composite yielded 6 g., B.P. 5-9 C. (I), and 12 g., B.P. 9-12.5" C. (II). Mass spectrometric analysis of II was satisfactory for (difluoromethyleneamino)sulfur pentafluoride, with the highest mass being the parent peak (211). The F n-m-r spectrum showed the presence of an SP and a CF group. Infrared analysis showed absorption at 5.58;). C=N), at 7.45 and.7.60,u ('C--'-F), and in the 11 to 12 region (SP Infrared analysis also showed that Cutl also was -90% SF5N=CF and 10 to 20% of SF NCF an isomer .of SF N=CF therefore, the

product was obtained in about a 45% conversion.

AfialySis.-Calcd.. for CF NS: F, 69.63; S, 16.75. Found; F, 68.50; S, 16.98.

3 Further evidence that the compound was SF N=CF was provided by formation of SF NHCF by the reaction with hydrogen fluoride at 80 C. and autogenous pressure. 1 1

Example VII "To a suspension of 168 g. of sodium fluoride in 500 m1. of tetramethylene sulfone was added 218 g of SF N CCI at ambient temperature. The mixture was heated to 60 C. in 0.35 hour, and then held'at.

214 hours, and the volatile product exiting through the.

water-cooled condenser was collected in a solid carbon dioxide-acetone cooled trap. Distillation of the volatile material yielded 14 g., 13.1. 57 C. (I), and 136 g,

7 B.P. 7 to 125 C., chiefly from'l0.5'to 12'.5 C. (II). Infrared analysis showed that II was about 95% (difluoromethyleneamino)sulfur pentafluoride, and 5% SF NCO; fraction I was about 80% SF N=CF with the remainder being chiefly SF NCO and an isomer of SF N=CF namely SF =NCF These analysis indicate a 73% conversion to product, based on the SF N=CCl used.

Careful redistillation of fraction II through a low temperature still yielded as the major fraction a product distilling at 10-12 C., which infrared analysis indicated was essentially pure SF N=CF free of SF NCQ. Pure SF N CF also has been obtained by gas chromatography using as the absorbent the ethyl ester of the acid obtained by telomerizing chlorotrifluoroethylene with methanol, followed by oxidation.

The SF N=CXX" compounds of this invention can be readily converted to perfluoroalkylamine sulfur pentafluorides by reaction with hydrogen fluoride, and aqueous formic acid, as illustrated in Examples A through D.

A mixture of 23 g. of SF N=CCl and 23 g. of hydrogen fluoride was heated at 7080 C. for two hours, under autogenous pressure, and then stored over sodium fluoride at room temperature and autogenous pressure to remove hydrogen chloride and unreacted hydrogen fluoride. Distillation of the product yielded 14.7 g., amounting to a 68% conversion, of SF NHCF (trifluoromethylamino)sulfur pentafluoride,- B.P. 28.5 to 31 C., and 1.9 -g., of a product with a B.P. 31.5 to 34 C. Mass spectrometric analysis showed a peak corresponding to the parent (211) and lower mass fragments which support the (trifluoromethylamino )sulfur penta fluoride structure. The infrared spectrum showed absorption at 2.88 and 6.80m (NH), at 838p CF), and at 1097 and 1134 (SF The F n-m-r spectrum indicated that an SP and a CF group were present.

Analysis..Calcd. for CHF NS: F, 72.04; s, 15.17. Found: F, 71.78; S, 15.91.

A 2 g. sample of (trifluoromethylamino)sulfur pentafluoride, prepared as above, was placed in a test tube. To it was then added 0.1 g. of high molecular weight polyoxymethylene prepared as in US. Pat. No. 2,768,994. The mixture was stoppered and allowed to stand at room temperature overnight. When examined, it was found that the polyoxymethylene had completely dissolved.

Cut No. B.P., C. Wt. (g.) Products 1 30-33. 5 2.46 so? I- 10 /11. 33. 541 4; is 5073 I; 50%; II. 41-44 1. 32' 20% I; 80% II. 4445. 1. 57 540% I; 90% II 45. s47. s. 35

Based on F n-m-r analyses- I Compound I was found to be SF N=C-FCF ,.(tetrafluoroethylideneamino)sulfur pentafluoride, while II was SF NHC F ('pentafluoroethylamino) sulfur pentafluoride; h 3 3 393. bas 9 h F19 'll z' dl lql 359% infrared spectrum showed absorption at 2.9 and 6.7; (NH), in the 8-9 (CF), and at 10.95 and 11.76;. (SP

Analysisr-Calcd. for C HF NS: F, 72.80. Founda Theinfraredspectrum of compound SF5N=CFCF3,'.

which comprised the major portion of Cut No. 1, showed absorption at 5.65;]. (-CF=N), in the 8-9 region (CF), and at 10.9,11. and 119; (SP The F n-m-r spectrum showed that after the peaks resulting from sr rurc r were eliminated, there remained peaks corresponding to an SP group, to a CF group, and to a CF bond, and the peaks were present in the expected ratios.

A mixture of 26 g. of SF N=CFC F and 11 g. of hydrogen fluoride was heated at -83 C. for 2.5 hours under autogenous pressure and then stored over sodium fluoride at room temperature and autogenous pressure for one hour to remove excess hydrogen fluoride. The product (27 g.) remaining attacked glass, so it was stored over 5 g. of fresh sodium fluoride pellets for an additional hour; 21 g. of liquidwas decanted from the pellets. Infrared analysis showed the crude product to contain 60-70% SF5N=CFC3F7, (octafluorobutylideneamino) sulfur pentafluoride, with the remainder being presumably SF NI IC F (nonafluorobutylamino)sulfur pentafluoride, since there was absorption at 2.9/L (NH) and at 6.75 Gas chromatographic analysis-' showed the presence of two major products, one product had a retention time of 2.65 minutes while the second had a retention time of 7.65 minutes. Attempts to remove the amine from the column were unsuccessful, since both products when removed from the column were shown both by mass spectrometric and infrared analyses to be SF N=CFC F (oetafluorobutylideneamino)sulfur pentafluoride.

In another experiment, a mixture of 46 g. o

and 40 g. of hydrogen fluoride was heated at C. for one hour, and at 200 .C. for one hour, and autogenous pressure in a Hastelloy C pressure reactor. The crude product, after storage over sodium fluoride pellets at room temperature and autogenous pressure for 24 hours, yielded 36 g. of liquid product, distilling above 25 C. The F n-rn-r spectrum showed the presence of two SP groups, a peak corresponding to N='= ]CF bond and additional CF peaks which probably resulted from the presence of a C F and a C 1 group. There was a single broad peak in the proton spectrum. By comparison with the F n-m-r spectrum of'a known sample of *Carrierl out on a 6' x 0.25 0D. stainless steel column, packeu with 20% by weight of a commercial silicone, sold as Silicone 200, supported'on 40 to 60 mesh acid washed fire brick. The column wasope 'ated at 24 C. with helium flowing at '60 col/minute, measured at the exit.

Reaction of (perfluoromethylamino)sulfur pentafluoride with silver (II) fluoride provides bis(trifluoromethyl)hydrazo-bis(sulfur pentafluoride) as shown in Example D, below.

Example D A mixture of 21 g. of SF NHCF and 50 g. of silver (II) fluoride was heated at 50 C. for one hour, 75 C. for one hour, and 100 C. for one hour and autogenous pressure in a 200 ml. stainless steel pressure reactor. The 21 g. of liquid recovered was distilled to give 2.72 g. of foreshot which infrared showed was chiefly product, B.P. 63101 C., and 15 g. (amounting to a 72% conversion) of (SF )CF NNCF (SF bis(trifluoromethyl) hydraZo-bis(sulfur pentafluoride), B.P. l01104 C., but chiefly at 103-104 C. The F n-m-r spectrum for the compound was satisfactory showing the presence of an SP and CF group. The highest peak showed a mass spectrum which corresponded to the parent minus SP (293), with lower peaks at 274 and 255, corresponding to additional losses of one and two fluorine atoms. The most abundant peaks in the spectrum corresponded to those for SP (127) and the CF (69) groups. The infrared spectrum showed absorption at 7.95 8.40 1, and 8.6041 (CF) and broad absorption in the 10.7 to 12.0 region (SP Analysis.Calcd. for CZFMNZSZ: F, S. 15.24. Found: F, 71.81; S, 15.44.

A test portion of the product was uneflected by boiling with NaOH solution one to two minutes.

Since obvious modifications and equivalents in the invention will be evident to those skilled in the chemical arts, I propose to be bound solely by the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula wherein X is a halogen of atomic number 9-17 and X is selected from the group consisting of halogen of atomic number 9-17, hydrogen-free polyfluoroalkyl of up to 19 carbons, aryl, chloroaryl, and nitroaryl of up to 14 carbons, SF N=CCl and SF N=CF.

2. (Dichloromethyleneamino)sulfur pentafluoride,

3. (1-chlorotrifluoroethylideneamino)sulfur pentafluoride, SF N=CClCF 4. (1-chloroheptafluorobutylidenearnino)sulfur pentafluoride, SF N=CClC F 5. N,N' (dichloroethanediylidene)bis(aminosulfur pentafluoride), SF N=CClCCl=NSF 6. (Phenylchloromethyleneamino)sulfur pentafluoride, SF N=CClC H 7. (Difluoromethyleneamino)sulfur pentafluoride,

8. (Trifluoromethylamino)sulfur pentafl-uoride.

9. The process of preparing a compound having the SF N=group which comprises reacting, under the influence of ultraviolet light, a mixture of SF Cl and a member of the group consisting of cyanogen, cyanogen halides and carbonitriles free of aliphatic hydrogen and carbon-carbon unsaturation and having the formula ACN wherein A is selected from the group consisting of polyfluoroalkyl of up to 19 carbons and aryl, chloroaryl and nitroaryl of up to 14 carbons.

10. The process of preparing SF N=CC1 which comprises reacting, under the influence of ultraviolet light, a mixture of SEQ and cyanogen chloride.

11. The process of preparing SF N=CCICF which comprises reacting, under the influence of ultraviolet light, a mixture of SF Cl and trifluoroacetonitrile.

12. The process of preparing SF N:CClC F which comprises reacting, under the influence of ultraviolet light, a mixture of SF Cl and perfluorobutyronitrilc.

13. The process of preparing SF N=CClCCl=NSF which comprises reacting, under the influence of ultraviolet light, a mixture of SEQ and cyanogen.

14. The process of preparing SF N=CClC H which comprises reacting, under the influence of ultraviolet light, a mixture of SF Cl and benzonitrile.

15. The process of replacing with fluorine the chlorine in a member of the group consisting of SF N=CCl SF N=CClCCl=NSF and SF N=CClR R being hydrogen-free polyfluoroalkyl of up to 19 carbons, which comprises reacting the same with an alkali metal fluoride at a temperature in the range of about -200 C. in an inert liquid reaction medium.

16. The process of preparing SF N=CF which comprises reacting SF N=CCi with an alkali metal fluoride at a temperature in the range 50200 C. and in a liquid reaction medium.

17. The process of preparing SF N=CF which comprises reacting SF N=CCl with sodium fluoride at a temperature in the range 50-200 C. and in a liquid reaction medium.

References Cited by the Examiner UNITED STATES PATENTS 2,862,029 11/1958 Smith 260-543 2,883,422 4/1959 Tullock 260-543 3,053,789 9/1962 De Witt 260-30.8 3,053,790 9/1962 Lewis et a1. 26030.8

OTHER REFERENCES Halpern et 211., Applied Spectroscopy, vol. 11, 1957, page 174.

Smith et al., I. Am. Chem. Soc., vol. 82, February 1960, pp. 551-555.

LORRAINE A. WEINBERGER, Primary Examiner.

LEON ZITVER, Examiner. 

1. A COMPOUND OF THE FORMULA
 9. THE PROCESS OF PREPARING A COMPOUND HAVING THE SF5-N= GROUP WHICH COMPRISES REACTING, UNDER THE INFLUENCE OF ULTRAVIOLET LIGHT, A MIXTURE OF SF5C1 AND A MEMBER OF THE GROUP CONSISTING OF CYANOGEN, CYANOGEN HALIDES AND CARBONITRILES FREE OF ALIPHATIC HYDROGEN AND CARBON-CARBON UNSATURATION AND HAVING THE FORMULA ACN WHEREIN A IS SELECTED FROM THE GROUP CONSISTING OF POLYFLUOROALKYL OF UP TO 19 CARBONS AND ARYL, CHLOROARYL AND NITROARYL OF UP TO 14 CARBONS.
 15. THE PROCESS OF REPLACING WITH FLUORINE THE CHLORINE IN A MEMBER OF THE GROUP CONSISTING OF SF5N=CCL2, SF5N=CCL-CCL=NSF5 AND SF5N=CCLRF,RF BEING HYDROGEN FREE POLYFLUOROALKYL OF UP TO 19 CARBONS, WHICH COMPRISES REACTING THE SAME WITH AN ALKALI METAL FLUORIDE AT A TEMPERATURE IN THE RANGE OF ABOUT 50-200* C. IN AN INERT LIQUID REACTION MEDIUM. 